Beta Carboline MAOIs - towards a more effective e-liquid

[DVap]

if you start with 100ml alkaloids and dissolve them in the mineral oil like you said, then re-extract to acid at 5.6...
remove the acidified water, basify and then extract back to fresh non polar, measure how much you get back. If it's >90ml, then we will know for certain that the single protonation site is creates enough of a preference for the acid phase.
There might still be issues with using the weaker organic acids, multiple kpa's etc... but it's one less easter egg.

Let's not sell weak organic acids short.

5% acetic acid isn't too shabby with a pKa of 4.76.
We can get the Ka easily enough as pKa = -log(Ka) or 4.76 = -log(Ka) or Ka = 0.0000174.
so [H+][CH3COO-] / [CH3COO3] = 0.0000174 and at 5% or 0.833N, we have [H+][CH3COO-]/[0.833] = 0.0000174. So [H+] = 0.003807.
And pH is simply -log(0.003807) or 2.42. (with one lazy shortcut that has little effect).

Citric acid is even stronger.

pKa1=3.09 (Ka=0.0008)
pKa2=4.75
pKa3=6.41

so 0.25 molar citric acid gives [H+][Citrate-] / undissociated = 0.0008 so [H+] = 0.014M or pH=1.85
and that's not even counting the added acidity of the weaker hydrogens.

So putting around 50g of citric acid into a liter of water gives a pH < 1.85

Not too shabby at all.

 

[deusXmchna]

not trying to threadjack with a discussion, merely a simple question, that I'm sure there's a simple answer to (and this seemed like the best place to get said answer):

Is steam distillation not a viable option in nicotine extraction?
I guess I shouldve googled it first, but figured the major Figures here had already slogged through the info, and had distilled an answer already

thanks

*waits quietly and patiently, hoping not to get a smackdown from the UberChemists*

Nevermind. Ran across DVaps thoughts re:steam distillation on another thread.
sorry!

 

[2cb]

Interesting. I think the desire to stop an analog comes from the fact that it starts to taste like crap the closer it is to being done. That's why I didnt and why I think most people don't chain smoke.
I think if you only had access to nasty tasting vape liquid, you'd feel done after ten hits.

i had the thought yesterday that the feeling to stop may be due to combustion by-product saturation of the blood, a lowered level of oxygen carrying capacity. i had the thought that one could smoke a cigarette worth of any plant material and feel "i don't want to smoke more ..." on the other hand, i am sure there is certain levels of "intoxication" that provide that feeling as vapers of other substances might note, but Nicotine alone doesn't provide it (at least for me). and then there might be a combination of those factors that terminate a desire to inhale more of a substance.

i don't mean to interrupt any conversation with my thoughts, but i don't really have time to search for all the right threads for each thought, and my main interest was aligned with additional alkaloid factors that would eliminate my desire for my 3-5 cigarettes per day that i keep hanging on to after a few months. it seems to occur in the morning when i awake, and before any big project i need to dive into. much of my past/early background is in chemistry and botany (later engineering), and i do not wish to offend with my ummm - well ... i know that i have offended because i don't seem to have the same emotional worries and fears about things as others. my nature is to expect people to use their own good judgment and deal with things unemotionally. i hope that is acceptable in a more scientific thread.

 

[kinabaloo]

Let's not sell weak organic acids short.

5% acetic acid isn't too shabby with a pKa of 4.76.
We can get the Ka easily enough as pKa = -log(Ka) or 4.76 = -log(Ka) or Ka = 0.0000174.
so [H+][CH3COO-] / [CH3COO3] = 0.0000174 and at 5% or 0.833N, we have [H+][CH3COO-]/[0.833] = 0.0000174. So [H+] = 0.003807.
And pH is simply -log(0.003807) or 2.42. (with one lazy shortcut that has little effect).

Citric acid is even stronger.

pKa1=3.09 (Ka=0.0008)
pKa2=4.75
pKa3=6.41

so 0.25 molar citric acid gives [H+][Citrate-] / undissociated = 0.0008 so [H+] = 0.014M or pH=1.85
and that's not even counting the added acidity of the weaker hydrogens.

So putting around 50g of citric acid into a liter of water gives a pH < 1.85

Not too shabby at all.

Could dissolve that 50g in 100ml (2.6M) and achieve a pH around 1.36 if required
That would be equivalent to about 0.044M HCl (0.1M HCl has a pH of 1.0)

Solubility of citric acid in water: 73 g/100 ml (20°C)

~~~

In lemons, the juice is about 5% citric acid / citrates, depending on ripeness and other factors (50g / 1000ml). Some of the acid is neutralised, however (some of the hydrogen citrate, if you will, is nuetralised to other citrates) and so the pH would be only about 2.3 in this case

 

[slopes]

Does this mean vinegar and citric acid are usable?

- I'm not sure lime is such a good idea... I've got some strange looking solids that keep forming and floating around in my juice. I syringe off the good stuff and then a day of so later it's there again.

 

[kinabaloo]

Does this mean vinegar and citric acid are usable?

- I'm not sure lime is such a good idea... I've got some strange looking solids that keep forming and floating around in my juice. I syringe off the good stuff and then a day of so later it's there again.

For single protonation of nicotine, yes. We will soon know if that is sufficient for our purposes; assuming this holds for the other alkaloids too. If double protonation is required (in the case of nicotine and maybe some other alkaloids) a lower pH will be required; I couldn't find the value for this in a quick search.

In other words, a 5% citric acid solution may retrieve only some of the nicotine / other alkaloids, or subset of other alkaloids (or, more precisely, more of some alkaloids than others).

Pure citric acid would definitely be preferable.

 

[slopes]

kinabaloo - are you making any more WTA? My pollen press arrived today (bought on Ebay), I think it will be a good replacement for the garlic press so I'm thinking about running another batch (although I know the actual need for pressing is still up for debate) - maybe this time I should use the pure citric acid?

 

[kinabaloo]

kinabaloo - are you making any more WTA? My pollen press arrived today (bought on Ebay), I think it will be a good replacement for the garlic press so I'm thinking about running another batch (although I know the actual need for pressing is still up for debate) - maybe this time I should use the pure citric acid?

I'm waiting on the citric acid effectiveness official report so to speak. But my hunch would be that a near saturated citric acid solution will do a reasonable if not perfect job (that's about 50-60% solution).

Nice unit you got there, I remember the picture

 

[kinabaloo]

The question also is : how little citric acid can we use while still getting an effective conversion (extracting the freebase alkaloids from the oil).

This can be calculated although the amount of alkaloids will not be known exactly. But one could make a good estimate and err on the side of slight excess of acid.

 

[kinabaloo]

"Nicotine is predominantly protonated at pH<8.2 and double protonated at pH<3.1"

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DVap gives a figure of pH 5.7 for complete (100% as opposed to 'predominantly' - maybe 51% or 90% ?) single protonation. pH 5.7 is also where duble protonation begins to occur.

From this, it would seem that vinegar or lime juice (though better 5% citric acid) should do the job, even if double protonation is required; though how well depends on the actual percentage that is 'predominantly' (at least 50%).

100% double protonation would be reached with a pH somewhere between 1 and 2. The exact figure will pop up soon but a 60% citric acid solution should enable somewhere around 80 - 100% double protonation.

~~~

In passing:
From same source : nicotine extraction (in their process, haven;t examined in depth but they used sodium hydroxide as the base) from vegetable matter at pH 6 is 0%, pH7 (distilled water) ~30%. At pH 11, over 95% (confirming the efficacy of sodium carbonate for freebasing the alkaloids in the tobacco leaf).

~~~

On the freebase / protonated (ionised) topic:
Some prior discussion and testing (primarily by DVap and Exogenesis) suggests that single protonated nicotine has much the same vape quality as freebase, and that seemingly the freebase form is created by the heating in the atomiser (at least when acidified with vinegar, which is likely better than citric acid for the heat decomposition products of any excess). Indeed, even the nicotine salts in solid form readily decompose on heating to yield freebase nicotine at quite low temperatures (120 - 200C, from memory).

The relevant posts starts about here : http://www.e-cigarette-forum.com/fo...-determining-nicotine-dvap-62.html#post675789

 

[kinabaloo]

The issue with the household type acids is not just about attaining the right pH (suffciently low pH) because these are organic acids and do not dissociate much in water to expose the acidic hydrogen ion (proton). This also means excess acid remains in the end-product. Problems: taste (vinegar); possible residues and/or thermal decomposition (citric acid).

 

[kinabaloo]

To use a high concentration of citric acid while avoiding (too much) excess acid in the end product, only a (very) small amount of the concentrated acid will be used relative to the oil. This would be difficult to separate but the VG can be added once the alkaloids have been protonated and had time to pass into the acidified water *needs more time when relative volume is small). It will then be much easier to separate the acidified water / alkaloids / VG mix from the oil.

edit : this might cause migration back to the oil if not done quickly, and its not easy as the VG and water would take time to mix, but we dont want to skake up with the oil present.

 

[tescela]

nope, didn't forget Kin.
I don't think anyone could possibly deny that you are the one that has kept this thread moving forward on all fronts.

+1 (this goes without saying, but let's say it anyway)

Maybe no-one can work it out because I'm not quite in the same boat as most people here.

What do you mean?

What's remarkable about WTA? The obvious thing really but it just crept up on me - and surprised me; with WTA I don't feel like having a smoke ! And since it's basically a liquid smoke, why would I ?

Now I am wondering: am I the only one that assumed this would be an inherent characteristic of effective WTA eliquid?

It has banished the cigarette cravings?

That's understadable, since the wta liquid is essentially a cigarette, just in liquid form. Sounds great to me.

It's like taking vitamin a is not a carrot and the wta liquid sounds like drinking a carrot smoothie instead of eating a carrot - different form of the exact same thing - not a synthetic replacement like vitamins or vaping current nic only juices.

Great analogy, Hotwire!

Here are my own observations of using my WTA from snus, and just last week from swedish snus. No cigarettes in 4 months and not a snus user so my first use of WTA literally knocked my socks off. There was a period of a couple days determining the correct strength to use and once I figured that out everything was/is great. Getting that proportion figured out was interesting, try it, have affects like scalp tingling, dizzy, relaxed, etc. then wait until they were gone and try again and find out they really weren't gone yet, so it took a few days.

I don't vape it straight, that was just too 'strong' for me and personally I want to use the least amount as needed in order to satisfy any cravings I may have. I've found this balance for me and it works out to just a few drops per day mixed into my regular ejuice. It's diluted now to the point I get no perceivable side affects but I do still get the (I'm done) feeling and no longer have to chain vape.

From my experience so far, it's not the nicotine that satisfies at all, it's more about the wta, and then add nicotine to the wta and it's compounded even more. My guess is that someone who is still smoking or using snus will have less affects.

A question I am paying attention to now is... is it more addicting? I believe it might be but do not know yet. I have a feeling that the ingredients in the wta are what makes us addicted (mentally). The biggest side affect now is I feel relaxed after vaping and have no desire whatsoever for a cigarette, even during stressful times. This is huge for me as vaping nic alone did not do this.

Anyway I wanted to add this observation to the collective minds in here and I'll keep an eye on my consumption and cravings.

As it is right now, after several different extractions, I have 100ml of concentrated wta in 5 different flavors which at this rate will last years, so I'm pretty happy, not counting the one absolutely horribe tasting bottle of thunders lol.

Excellent, detailed feedback about your experience, Virk!

I don't recall what WTA method you used. Can you take a moment to point me to your methodology (assuming you posted it already)?

I know this much, it works for me, and such a low 'dose' or concentration, it's really unbelievable. Now to see if I want more as time goes on is what I'm watching for now, I expect it will happen.

This will be valuable information. Going forward, let's all please share feedback about whether your "satiation threshold" with WTA eliquid strength rises over time.

correction... I don't actually know it's 20% / 80%, thats actually incorrect, it's 100% distilled water.

Who's on first?

 

[kinabaloo]

One would want the citric acid a little less than saturated, to leave space for the alkaloids so to speak. So 50g in 100ml distilled water (pH ~1.35) should be a suitable acid solution. Should grab at least 80% of the alkaloids from the oil, if not 90%+.

~~~

Now, if you had 100mg of alkaloids in the oil, how much of this citric acid solution is required ? I guess twice the number of molecules for double protonation (and working only the most acidic hydrogen in citric acid). So now its a matter of looking up molecular weights ...

After all that, it going to be a very small volume. So hopefully single protonation will be sufficicient as then we can use a manageable volume of acid without too much excess acid in the end product (can be more dilute)

Rock and hard place, somewhat for the inorganic acids, although theoretically pretty effective, maybe wholly so.

On the other hand, if single protonation only is required, we're home and dry.

~~~

Thinking over tceight's riginal method, it would seem that he was single protonating, so maybe that is sufficient.

 

[DVap]

Might as well post this PDF.

The page of interest is page 4 of the PDF (page 147 of the journal within the PDF).

Haven't taken a close look in awhile, I found this when I was researching the nicotine titration way back and the data screamed "Use bromothymol blue!".

When it comes to full protonation/deprotonation, pH 1 and pH 10 pretty much take it to 100%. Anything <1 or >10 is overkill.

pH 2 and pH 9 are pretty damn close (probably 95% or so).

My gut says that the solubility behavior of nicotine will be driven by the much more basic pyrrolidine nitrogen. I will *try* to get to checking the polar -vs- nonpolar solubility behavior of the alkaloids at ~ pH 5, but the neurosurgeon just told I've got a disc in my neck that could stand to come out and that's pretty short-term nasty. I've been watching videos of the procedure all evening on Youtube, and it's put me off my dinner, and will probably be good for me saying the hell with breakfast and lunch tomorrow.

Let the over-analysis begin!

 

[kinabaloo]

"My gut says that the solubility behavior of nicotine will be driven by the much more basic pyrrolidine nitrogen." * That's why we need you DVap, for this depth of understanding.

Best wishes with your neck.

~~~

I think this suggests that single protonation would be sufficient to get most of the alkaloids (at least the nicotine). I just added to an earlier post that I think tceight was single protonating.

 

[DVap]

One would want the citric acid a little less than saturated, to leave space for the alkaloids so to speak. So 50g in 100ml distilled water (pH ~1.35) should be a suitable acid solution. Should grab at least 80% of the alkaloids from the oil, if not 90%+.

~~~

Now, if you had 100mg of alkaloids in the oil, how much of this citric acid solution is required ? I guess twice the number of molecules for double protonation (and working only the most acidic hydrogen in citric acid). So now its a matter of looking up molecular weights ...

After all that, it going to be a very small volume. So hopefully single protonation will be sufficicient as then we can use a manageable volume of acid without too much excess acid in the end product (can be more dilute)

Rock and hard place, somewhat for the inorganic acids, although theoretically pretty effective, maybe wholly so.

On the other hand, if single protonation only is required, we're home and dry.

~~~

Thinking over tceight's riginal method, it would seem that he was single protonating, so maybe that is sufficient.

Molarity-wise, it will take very little acid to overwhelm the alkaloids. ~0.25 M citric acid contains 0.25 millimoles/mL. 100 mg of alkaloids represents about 0.6 millimoles of alkaloids... so just a few mL of 0.25 M citric acid should do the trick.

 

[kinabaloo]

The pKa is the key not the pH, is that right?

 

[DVap]

"My gut says that the solubility behavior of nicotine will be driven by the much more basic pyrrolidine nitrogen." * That's why we need you DVap, for this depth of understanding.

Best wishes with your neck.

~~~

I think this suggests that single protonation would be sufficient to get most of the alkaloids (at least the nicotine). I just added to an earlier post that I think tceight was single protonating.

Thanks, the whole neck thing is a pain in the.. dammit. That doesn't sound right.

Heh.. I'd not done a calculation using Ka in maybe 25 years before yesterday... and I remember what a pain it was in qualitative organic to get those just right. No wonder I like strong acids and bases.

 

[kinabaloo]

Thanks, the whole neck thing is a pain in the.. dammit. That doesn't sound right.

Heh.. I'd not done a calculation using Ka in maybe 25 years before yesterday... and I remember what a pain it was in qualitative organic to get those just right. No wonder I like strong acids and bases.

But 0.25M might have a pH that is not sufficiently low.

Havng enough molecules with enough activation energy is not the correct thinking i guess, because it's not really a reaction, just ions in solution; so the pH is the key. Anywhere close ?